Catalyst of polymerization, copolymerization and oligomerization of olefins and drolefins

Abstract

A catalyst for polymerization, copolymerization and oligomerization of olefins and diolefins is described, which is a compound having the general formula MX n wherein M is a metal belonging to IVA -- VIA groups of the Periodic System or a cobalt, X is a halogen, hydrogen, cyclopentadienyl, alkoxy-, aryloxy-, or amido group, and n is an integer denoting the valency of M; a compound having the general formula M'R p Z k-p wherein M' is a metal of I--III groups of the Periodic System, R is a hydrocarbon radical, Z is a halogen, hydrogen, alkoxy-, aryloxy- or amido group, k is an integer denoting the valency of M', 1≦p≦k; or compound having the general formula MR m X n-m , wherein 2≦m≦n, said component being chemically bonded with the surface of a carbon-chain polymer carrier through the fragment ##STR1## WHEREIN R' = H, CH 3 , C 2 H 5 , CH 2 = CH 2 , C 6 H 5 ; R" = h, or CH 3 ; R"' = h, or CH 3 ; y = OH, NHR', SR; COCH 3 , CH 2 OH ##STR2## CH 2 NHR', COOH, OCOCH 3 , CH 2 SH, COOCH 3 , C .tbd. N, N(R') 2 , SO 2 R', SOR', --CH 2 --S--CH 2 --CH═CH 2 ,--CH 2 --NH--CH 2 --CH═CH 2 ,--CH 2 --SO 2 --CH 2 --CH═CH 2 , wherein R' is defined above, T is the degree of polymerization equal to 4 - 5000. In the case where use is made of compound MX n applied to a carbon-chain polymer carrier, it is activated with compound M'R p Z k-p , while in the case of use being made of compound M'R p Z k-p applied to a carbon-chain polymer carrier, it is activated with compound MX n . Said catalyst is several times (5 to 100) more active than prior art catalysts and provides for a high yield of the product, which may be as high as 1000 kg/g of a transition metal.

What is claimed is: 
     
       1. A catalyst of polymerization, copolymerization and oligomerization of olefins and diolefins, which is one of the following components: component A having the general formula MX n  wherein M is a metal belonging to IVA-VIA groups of the Periodic System or cobalt, X is a halogen, hydrogen, cyclopentadienyl, alkoxy-, aryloxy- or amide group, and n is an integer denoting the valency of M; component B which is an organometallic compound having the general formula M'R p  Z k-p  wherein M' is a metal belonging to I - III groups of the Periodic System, R is a hydrocarbon radical, z is a halogen, hydrogen, alkoxy-, aryloxy- or amide group, and k is an integer denoting the valency of M', 1≦p≦k; and component C which is a product having the general formula MR m  X n-m' , wherein n is an integer, 2≦m≦n, said component being chemically bonded to the surface of one of the fragments of the carbon-chain polymer carrier having grafted thereto substituents having the formula ##STR69## wherein: R' = H, CH 3 , C 2  H 5 , CH 2  = CH, or C 6  H 5  ; R" = h, or CH 3  ;   R"' = h, or CH 3  ;   Y = oh, nhr', sr', coch 3 , ch 2  oh, ##STR70## ch 2  nhr', ch 2  sh, cooh, ococh 3 , cooch 3 ,c .tbd. n, n(r') 2'  --so 2  r', --sor', --ch 2  --s--ch 2  --ch═ch 2 , --ch 2  --nh--ch 2  ch═ch 2 , --ch 2  --so 2  --ch 2  --ch═ch 2 , ##STR71## wherein R' is as defined above, t is a mean degree of polymerization, equal to 4-5000, and, after bonding, component A is in mixture with compound M'R p  Z k-p  and component B is in mixture with compound MX n .   
     
     
       2. A catalyst as claimed in claim 1, wherein the molar ratio between M', in M'R p  Z k-p , and M, in component A, is 5 to 500, preferably 10 to 100. 
     
     
       3. A catalyst in claim 1, wherein the molar ratio between M', in component B, and M, in MX n , is 20 to 200, preferably 50 to 100. 
     
     
       4. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR72## in which t = 50 to 1500, with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R p  Z k-p . 
     
     
       5. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR73## in which t = 100 to 2000, with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R p  Z k-p . 
     
     
       6. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR74## in which t = 30 to 300, with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R p  Z k-p . 
     
     
       7. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR75## in which t = 4 to 9, with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R P  Z k-p . 
     
     
       8. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR76## in which t = 4 to 9, with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R p  Z k-p . 
     
     
       9. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR77## in which t = 4 to 9, with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R p  Z k-p . 
     
     
       10. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR78## in which t = 500 to 2000, with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R p  Z k-p . 
     
     
       11. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR79## in which t = 4 to 9, with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R p  Z k-p . 
     
     
       12. 
     
     
       12. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR80## in which t = 4 to 9, with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R p  Z k-p . 
     
     
       13. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR81## in which t = 4 to 9, with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R p  Z k-p . 
     
     
       14. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR82## in which t = 100 to 2000, with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R p  Z k-p . 
     
     
       15. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR83## in which t = 500 to 2000, with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R p  Z k-p . 
     
     
       16. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR84## in which t = 500 to 5000, with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R p  Z k-p . 
     
     
       17. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR85## in which t = 500 to 5000, with the surface of a polymer carrier, in admixture with one of said organometallic compunds having the formula M'R p  Z k-p . 
     
     
       18. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR86## in which t = 400 to 4000, with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R p  Z k-p . 
     
     
       19. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR87## in which t = 50 to 1500, with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R p  Z k-p . 
     
     
       20. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR88## in which t = 500 to 2000 with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R p  Z k-p . 
     
     
       21. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR89## in which t = 4 to 9, with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R p  Z k-p . 
     
     
       22. A catalyst as claimed in claim 1, wherein used as component A is a compound having said formula MX n , chemically bonded through the fragment ##STR90## in which t = 4 to 9, with the surface of a polymer carrier, in admixture with one of said organometallic compounds having the formula M'R p  Z k-p . 
     
     
       23. A catalyst as claimed in claim 1, wherein used as component B is an organometallic compound having said formula M'R p  Z k-p , chemically bonded through the fragment ##STR91## in which t = 500 to 2000, with the surface of a polymer carrier, in admixture with a compound having the formula MX n . 
     
     
       24. A catalyst as claimed in claim 1, wherein used as component B is an organometallic compound having said formula M'R p  Z k-p , chemically bonded through the fragment ##STR92## in which t = 100 to 2000, with the surface of a polymer carrier, in admixture with a compound having the formula MX n . 
     
     
       25. A catalyst as claimed in claim 1, wherein component C is the product of interaction of MX n  and M'R p  Z k-p , having the formula MR m  X n-m , in which M, X, n, M', m, R, Z, p and k have values according to claim 1, and chemically bonded through the fragment ##STR93## in which t = 4 to 9, with the surface of a polymer carrier. 
     
     
       26. A catalyst as claimed in claim 1, wherein component C is the product of interaction of MX n  and M'R p  Z k-p , having the formula MR m  X n-m  and chemically bonded through the fragment ##STR94## in which t = 4 to 9, with the surface of a polymer carrier.